Binding of Butadiene Molecules Mediated by Ni Atom and Ni+ Ion

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2004-06, Vol.108 (24), p.5234-5241
• Main Authors: Kandalam, Anil K, Rao, B. K, Jena, P, Lilly, A. C
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp040009d

Theoretical ab initio calculations based on density functional theory including gradient corrections have been performed to study the binding of cis- and trans-1,3-butadiene molecules mediated by Ni atom and Ni+ ion. The geometries and dissociation energies are calculated to study the importance of Ni in the binding process. In the equilibrium geometry of Ni(butadiene) complex, the metal atom is found to position itself above the butadiene molecule and is bonded to all the carbon atoms in both the isomers of butadiene. The neutral and cationic Ni(butadiene)2 complexes prefer three-dimensional structures with the Ni atom/ion sandwiched between the two butadiene molecules. This leads to the embedding of Ni atom or Ni+ ion between the butadiene molecules during the binding process. The ground-state geometries of these complexes are stable against dissociation into smaller complexes, with Ni+(butadiene) complex being the most stable one among all the complexes studied.